Atomic Spectroscopy Reference Books: 1) Analytical Chemistry by Gary D. Christian 2) Principles of instrumental Analysis by Skoog, Holler, Crouch 3) Fundamentals of Analytical Chemistry by Skoog 4) Basic Concepts of analytical Chemistry by S. M. Khopkar We consider two types of optical atomic spectrometric methods that use similar techniques for sample introduction and atomization. The first is atomic absorption spectrometry (AAS), which for half a century has been the most widely used method for the determination of single elements in analytical samples. The second is atomic fluorescence spectrometry (AFS), which since the mid-1960s has been studied extensively. By contrast to the absorption method, atomic fluorescence has not gained widespread general use for routine elemental analysis. Thus, although several instrument makers have in recent years begun to offer special- purpose atomic fluorescence spectrometers, the vast majority of instruments are still of the atomic absorption type. Sample Atomization Techniques We first describe the two most common methods of sample atomization encountered in AAS and AFS, flame atomization, and electrothermal atomization. We then turn to three specialized atomization procedures used in both types of spectrometry. Flame Atomization In a flame atomizer, a solution of the sample is nebulized by a flow of gaseous oxidant, mixed with a gaseous fuel, and carried into a flame where atomization occurs. As shown in Figure, a complex set of interconnected processes then occur in the flame. The first step is desolvation, in which the solvent evaporates to produce a finely divided solid molecular aerosol. The aerosol is then volatilized to form gaseous molecules. Dissociation of most of these molecules produces an atomic gas. Some of the atoms in the gas ionize to form cations and electrons. Other molecules and atoms are produced in the flame as a result of interactions of the fuel with the oxidant and with the various species in the sample. As indicated in Figure, a fraction of the molecules, atoms, and ions are also excited by the heat of the flame to yield atomic, ionic, and molecular emission spectra. With so many complex processes occurring, it is not surprising that atomization is the most critical step in flame spectroscopy and the one that limits the precision of such methods. Because of the critical nature of the atomization step, it is important to understand the characteristics of flames and the variables that affect these characteristics. Types of Flames Table 9-1 lists the common fuels and oxidants used in flame spectroscopy and the approximate range of temperatures realized with each of these mixtures. Note that temperatures of 1700°C to 2400°C occur with the various fuels when air is the oxidant. At these temperatures, only easily decomposed samples are atomized, so oxygen or nitrous oxide must be used as the oxidant for more difficult to atomize samples (refractory samples). These oxidants produce temperatures of 2500°C to 3100°C with the common fuels. The burning velocities listed in the fourth column of Table 9-1 are important because flames are stable only in certain ranges of gas flow rates. If the gas flow rate does not exceed the burning velocity, the flame propagates back into the burner, giving flashback. As the flow rate increases, the flame rises until it reaches a point above the burner where the flow velocity and the burning velocity are equal. This region is where the flame is stable. At higher flow rates, the flame rises and eventually reaches a point where it blows off the burner. With these facts in mind, it is easy to see why it is very important to control the flow rate of the fuel-oxidant mixture. This flow rate very much depends on the type of fuel and oxidant being used. Flame Structure As shown in Figure 9-2, important regions of a flame include the primary combustion zone, the interzonal region, and the secondary combustion zone. The appearance and relative size of these regions vary considerably with the fuel-to-oxidant ratio, the type of fuel and oxidant, and the type of burner. The primary combustion zone in a hydrocarbon flame is recognizable by its blue luminescence arising from the band emission of C2, CH, and other radicals. Thermal equilibrium is usually not achieved in this region, and it is, therefore, rarely used for flame spectroscopy. The interzonal area, which is relatively narrow in stoichiometric hydrocarbon flames, may reach several centimeters in height in fuel-rich acetylene-oxygen or acetylene– nitrous oxide sources. Because free atoms are prevalent in the interzonal region, it is the most widely used part of the flame for spectroscopy. In the secondary reaction zone, the products of the inner core are converted to stable molecular oxides that are then dispersed into the surroundings. A flame profile provides useful information about the processes that go on in different parts of a flame; it is a contour plot that reveals regions of the flame that have similar values for a variable of interest. Some of these variables include temperature, chemical composition, absorbance, and radiant or fluorescence intensity. Flame Absorption Profiles. Figure 9-4 shows typical absorption profiles for three elements. Magnesium exhibits a maximum in absorbance at about the middle of the flame because of two opposing effects. The initial increase in absorbance as the distance from the base increases results from an increased number of magnesium atoms produced by the longer exposure to the heat of the flame. As the secondary combustion zone is approached, however, appreciable oxidation of the magnesium begins. This process eventually leads to a decrease in absorbance because the oxide particles formed do not absorb at the observation wavelength. To achieve maximum analytical sensitivity, then, the flame must be adjusted up and down with respect to the beam until the region of maximum absorbance is located. The behavior of silver, which is not easily oxidized, is quite different. As shown in Figure 9-4, a continuous increase in the number of atoms, and thus the absorbance, is observed from the base to the periphery of the flame. By contrast, chromium, which forms very stable oxides, shows a continuous decrease in absorbance beginning close to the burner tip; this observation suggests that oxide formation predominates from the start. These findings suggest that a different portion of the flame should be used for the determination of each of these elements. The more sophisticated instruments for flame spectroscopy are equipped with monochromators that sample the radiation from a relatively small region of the flame, and so a critical step in the optimization of signal output is the adjustment of the position of the flame with respect to the entrance slit. Flame Atomizers Flame atomizers are used for atomic absorption, fluorescence, and emission spectroscopy. Figure 9-5 is a diagram of a typical commercial laminar-flow burner that uses a concentric- tube nebulizer. The aerosol, formed by the flow of oxidant, is mixed with fuel and passes a series of baffles that remove all but the finest solution droplets. The baffles cause most of the sample to collect in the bottom of the mixing chamber where it drains to a waste container. The aerosol, oxidant, and fuel are then burned in a slotted burner to provide a 5- to 10‑cm high flame. Laminar-flow burners produce a relatively quiet flame and a long path length for maximizing absorption. These properties tend to enhance sensitivity and reproducibility in AAS. The mixing chamber in this type of burner contains a potentially explosive mixture that can flash back if the flow rates are too low. Fuel and Oxidant Regulators. An important variable that requires close control in flame spectroscopy is the flow rate of both oxidant and fuel. It is desirable to be able to vary each over a broad range so that optimal atomization conditions can be determined experimentally. Fuel and oxidant are usually combined in approximately stoichiometric amounts. For the determination of metals that form stable oxides, however, a flame that contains an excess of fuel is often desirable. Flow rates are usually controlled by means of double-diaphragm pressure regulators followed by needle valves in the instrument housing. A widely used device for measuring flow rates is the rotameter, which consists of a tapered, graduated, transparent tube that is mounted vertically with the smaller end down. A lightweight conical or spherical float is lifted by the gas flow; its vertical position is determined by the flow rate. Newer AAS instruments feature computer control over fuel and oxidant flows and flame ignition. In addition, computer control enables many safety features to be implemented such as not allowing ignition under many unsafe conditions. Performance Characteristics of Flame Atomizers. Flame atomization is the most reproducible of all liquid-sample-introduction methods that have been developed for AAS to date. The sampling efficiency of other atomization methods and thus the sensitivity, however, are markedly better than in flame atomization. There are two primary reasons for the lower sampling efficiency of the flame. First, a large portion of the sample flows down the drain. Second, the residence time of individual atoms in the optical path in the flame is brief (,10–4 s). Electrothermal Atomization Electrothermal atomizers, which first appeared on the market in the early 1970s, generally provide enhanced sensitivity because the entire sample is atomized in a short period, and the average residence time of the atoms in the optical path is a second or more. Electrothermal atomizers are used for atomic absorption and atomic fluorescence measurements but have not been generally applied for direct production of emission spectra. They are also used for vaporizing samples in inductively coupled plasma emission spectroscopy, however.